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CN-121983594-A - Heteroatom-modulated diatomic catalyst, and preparation method and application thereof

CN121983594ACN 121983594 ACN121983594 ACN 121983594ACN-121983594-A

Abstract

The invention relates to the technical field of catalytic materials, in particular to a heteroatom-modulated diatomic catalyst, a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing binuclear metal complex molecules, zinc salt and an organic solvent, stirring and mixing the obtained mixed solution and a 2-methylimidazole solution under a dark condition, and performing heat treatment on the obtained composite material to obtain the heteroatom-modulated diatomic catalyst. The introduction of the hetero atoms not only can enhance the stability of the double-atom sites and prevent the double-atom sites from agglomerating in the heat treatment and electrochemical processes, but also can finely regulate and control the electronic structure of the double-core center of the double atoms through the unique geometrical and electronic effects thereof to generate a strong catalytic effect, thereby obviously improving the intrinsic activity and stability of the double-core metal complex on the ORR.

Inventors

  • XU QIANG
  • ZHANG FANCHAO
  • XIAO XIN

Assignees

  • 南方科技大学

Dates

Publication Date
20260505
Application Date
20251211

Claims (10)

  1. 1. A method for preparing a heteroatom-modulated diatomic catalyst, comprising the steps of: mixing binuclear metal complex molecules, zinc salt and an organic solvent to obtain a mixed solution; mixing 2-methylimidazole with an organic solvent to obtain a 2-methylimidazole solution; Stirring and mixing the mixed solution and the 2-methylimidazole solution under a light-shielding condition to obtain a composite material; And carrying out heat treatment on the composite material to obtain the heteroatom-modulated diatomic catalyst.
  2. 2. The method for preparing a heteroatom-modulated diatomic catalyst according to claim 1, wherein said binuclear metal complex molecule is selected from one or more of bis-tetra-p-chlorophenyl iron porphyrin, bis-p-chlorophenyl manganese porphyrin, [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, [1,1' -bis (diphenylphosphino) ferrocene) ] nickel dichloride, (1, 1' -bis (diphenylphosphino) ferrocene) cobalt dichloride, manganese m-oxo-bis-p-chlorophenyl porphyrin, [ μ -C 6 H 4 -1,2-(κ 2 -S) 2 ][Fe 2 (CO) 6 ].
  3. 3. The method for preparing a heteroatom-modulated diatomic catalyst according to claim 1, wherein the zinc salt is selected from one or more of zinc nitrate, zinc acetate and zinc chloride, and the organic solvent is selected from one or more of methanol, ethanol, isopropanol, N-dimethylformamide, N-diethylformamide, N-methylpyrrolidone and dimethylsulfoxide.
  4. 4. The method of preparing a heteroatom-modulated diatomic catalyst according to claim 1, characterized in that the molar ratio of said binuclear metal complex molecules to said zinc salts is (0.01-0.05): 4-12.
  5. 5. The method for preparing a heteroatom-prepared diatomic catalyst according to claim 1, wherein the concentration of said 2-methylimidazole solution is 0.3mmol/mL-1mmol/mL.
  6. 6. The method for preparing a heteroatom-prepared diatomic catalyst according to claim 1, wherein after stirring and mixing the mixed solution and the 2-methylimidazole solution under the condition of avoiding light, further comprising: centrifuging or vacuum filtering to obtain precipitate; And drying the precipitate at 40-80 ℃ to obtain the composite material.
  7. 7. The method for preparing a heteroatom-modulated diatomic catalyst according to claim 1, wherein the heating rate of the heat treatment is 2 ℃ to 8 ℃ per minute, the temperature of the heat treatment is 900 ℃ to 1100 ℃, and the time of the heat treatment is 1h to 3h.
  8. 8. The method for preparing a heteroatom-modulated diatomic catalyst according to claim 1, characterized in that the heat treatment is performed under an inert atmosphere; preferably, argon is introduced into the heat treatment to provide inert atmosphere, and the flow rate of the argon is 50SCCM-120SCCM.
  9. 9. A heteroatom-formulated diatomic catalyst, characterized in that it is produced by a process for the preparation of a heteroatom-formulated diatomic catalyst according to any of claims 1-8.
  10. 10. Use of the heteroatom-modulated bi-atomic catalyst of claim 9 in a metal-air battery.

Description

Heteroatom-modulated diatomic catalyst, and preparation method and application thereof Technical Field The invention relates to the technical field of catalytic materials, in particular to a heteroatom-modulated diatomic catalyst, a preparation method and application thereof. Background Commercial application of zinc-air batteries is largely limited by the slow kinetics of the oxygen reduction reaction (Oxygen Reduction Reaction, ORR) that occurs at their air cathode. The ORR process involves multiple steps of complex electron transfer, and its slow reaction rate results in a battery with critical bottlenecks of high charge-discharge overpotential, low energy efficiency, insufficient power density, and short cycle life. Diatomic Catalysts (DACs) are receiving increasing attention as an emerging front-end catalytic system. DACs, particularly homonuclear diatomic Catalysts (such as Fe 2), not only inherit the advantage of high atomic utilization of Single-Atom Catalysts (SACs), but also exhibit synergistic catalytic effects that Single-Atom sites do not possess because two adjacent metal atoms can form unique binuclear active centers. The synergistic effect can effectively change the reaction path, optimize the adsorption/desorption actions on key reaction intermediates, and even directly crack O-O bonds, thereby being expected to obviously reduce the reaction energy barrier of ORR and promote the catalytic activity and selectivity. Despite its broad prospects, precise synthesis and electronic structure regulation of diatomic catalysts still face significant challenges, including how to prevent migration and agglomeration of metal atoms, and fine regulation of the local coordination environment of the constructed diatomic sites. Accordingly, the prior art is still in need of improvement and development. Disclosure of Invention In view of the shortcomings of the prior art, the invention aims to provide a heteroatom-modulated diatomic catalyst, and a preparation method and application thereof, and aims to solve the problem that the existing technology for preparing the diatomic catalyst cannot effectively prevent metal migration and agglomeration. The technical scheme of the invention is as follows: A method for preparing a heteroatom-modulated diatomic catalyst comprising the steps of: mixing binuclear metal complex molecules, zinc salt and an organic solvent to obtain a mixed solution; mixing 2-methylimidazole with an organic solvent to obtain a 2-methylimidazole solution; Stirring and mixing the mixed solution and the 2-methylimidazole solution under a light-shielding condition to obtain a composite material; And carrying out heat treatment on the composite material to obtain the heteroatom-modulated diatomic catalyst. The preparation method of the heteroatom-modulated diatomic catalyst, wherein the binuclear metal complex molecule is selected from one or more of bis-tetra-p-chlorophenyl iron porphyrin, bis-tetra-p-chlorophenyl manganese porphyrin, [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, [1,1' -bis (diphenylphosphino) ferrocene) ] nickel dichloride, (1, 1' -bis (diphenylphosphino) ferrocene) cobalt dichloride, manganese m-oxo-bis-p-chlorophenyl porphyrin and [ mu-C 6H4-1,2-(κ2-S)2][Fe2(CO)6 ]. The preparation method of the heteroatom-modulated diatomic catalyst comprises the steps of selecting zinc salt from one or more of zinc nitrate, zinc acetate and zinc chloride, and selecting organic solvent from one or more of methanol, ethanol, isopropanol, N-dimethylformamide, N-diethylformamide, N-methylpyrrolidone and dimethyl sulfoxide. The preparation method of the heteroatom-modulated diatomic catalyst comprises the step of (4-12) mixing the binuclear metal complex molecule with the zinc salt in a molar ratio of (0.01-0.05). The preparation method of the heteroatom-prepared diatomic catalyst comprises the step of preparing the heteroatom-prepared diatomic catalyst, wherein the concentration of the 2-methylimidazole solution is 0.3mmol/mL-1mmol/mL. The preparation method of the heteroatom-prepared diatomic catalyst, wherein after stirring and mixing the mixed solution and the 2-methylimidazole solution under the light-shielding condition, further comprises: centrifuging or vacuum filtering to obtain precipitate; And drying the precipitate at 40-80 ℃ to obtain the composite material. The preparation method of the heteroatom-modulated diatomic catalyst comprises the steps of heating at a temperature of 2-8 ℃ per minute, heating at 900-1100 ℃ for 1-3 h. The preparation method of the heteroatom-modulated diatomic catalyst, wherein the heat treatment is performed under an inert atmosphere; preferably, argon is introduced into the heat treatment to provide inert atmosphere, and the flow rate of the argon is 50SCCM-120SCCM. A heteroatom-modulated diatomic catalyst is prepared by a heteroatom-modulated diatomic catalyst preparation method. Use of a heteroatom-modulated diatomic catalyst in a met